Sulphuric acid derivative of alkyl phenols



Fatented es. 235, 3194i 2,267,658? sumac acm nnarrvn or ALKYL reasons Lucas ll. Kyr'ides, Webster Groves, Mm, assignor to Monsanto Checal Company, St. Louis, Mo., a corporation of Delaware No Drawing. Application September 26, 1939, {serial No. 296,673

(oi. eta-512) This invention relates to the alkylation of phenols and it has particular relation to alkylation thereof by means of unsaturated hydrocarbons.

The object of the invention is to prepare alkali metal salts of the sulphuric acid derivative of an alkyl phenol wherein the alkyl group corresponds to an acyclic hydrocarbon polymer having a molecular weight between about 100 and about 224.

It has also been noted that these sulphonated products form valuable moth proofing agents, detergents or wetting agents, or they may be condensed with aldehydes to provide oil soluble artificial resins of the Bakelite" type. However, no entirely satisfactory method of preparing these alkylated phenols has heretofore been available.

A method heretofore preferred, of preparation of these compounds involves alkylation of phenols with tertiary unsaturated hydrocarbons in the presence of large (approximately molar) amounts of sulphuric acid as a carrier for the unsaturated hydrocarbon. British patent 409,111 discloses alkylation of phenols with unsaturated olefines using as low as 0.075 mol of sulphuric acid to catalyze the reaction. However, such processes, even with the latter amounts or acid, have been found to be objectionable because the use of large amounts of sulphuric acid entails a considerable item of expense and entails ether and resin formation at elevated temperatures. Moreover, where such processes were employed it was necessary to split off the sulphonic acid group that forms and neutralize this acid with sodium carbonate at the end of the reaction, and then to wash out the salts with water or other solvent. This, oi course, involved additional expense and labor, and resulted in a loss of some of the product. The process was also objectionable because, as noted in the patent/even at moderate temperatures of 70 C. or 80 C. it tended to induce formation of resins and sulphonic acids. Even with the concentrations of acid specified in the British patent above noted, working temperatures of about 25 C, are recommended and apparently if the temperature exceeded 70 0.;

formation of resins, ethers and the like was excessive. In an article by Natelson (J. A. (3. 8.,

vol. 56, page 1585) temperatures below 10 C. are recommended.

The present invention involves the discovery that a mere trace of strongly acid material, such as sulphuric acid, sulphonic. acid or other strong- 1y acid materials or salts thereof with weak bases,

- tion of two or more molecules of a tertiary olefine,

such as isobutylene or tertiary amylene, and the influence of heat, a trace of strongly acidic material and preferably in the presence of an excess of phenol may readily be reacted to form the corresponding mono tertiary alkyl phenols.

It also involves the discovery that orthoalkylated phenols may, at will, be converted into para compounds merely by'subjecting them to heat in the presence of traces of strongly acidic materials.

In this process of preparing alkylated phenols, the reaction may be carried out at ordinary temperatures and up to the boiling point of the phenol under atmospheric pressure, and if pressure is used, still higher temperatures may be employed. The lower temperatures of reaction (around 40 C. or C. or lower) favor the formation of the ortho-alkylated phenol, while higher temperatures favor the formation of the 7 para compound. An excess of phenol in the reaction is found to promote the formation of the mono-alkylated compounds, while in the presence of molar ratios of the components, large amounts or I the di-alkylated (RZCGHBOH compounds) phenol are also formed.

The merest trace of a strongly acidic material such as sulphuric acid is effective in causing the reaction and in general approximately one drop of concentrated acid per g. of phenol is sufilcient. The quantity may even beas low as about one drop for three or four hundred grams of phenol and excellent results are obtained with approximately 0.0005% of acid based upon the weight of phenol and it should not exceed ap proximately 1% upon the same basis.

The following constitute specific examples-of applications of the principles of the invention:

Example 1.-Phenol and di-isobutylene in the ratio of 800 grams of the former to 151 grams of the latter are heated with 8 drops of sulphuric acid (concentrated) in a glass container at a proximately 22 hours.

proximately 0.5 gram) is added to neutralize any .di-isobutyl phenol.

- The residue weighs only about 2 grams, showing of the orderof 140 C.-170 0., more or' temperature of about 120 C. for a period of -ap-,

Sodium carbonate (aptrace of acid present and the mixture is subjected directly to fractionation under vacuum. At a A 7 pressure of 28 mm. absolute excessphenol distills 011 within a temperature range of 95 C.-130 C.

Between 130 C.-160 C. 6 grams of a liquid fraction comes over which-may contain the ortho- The para di-isobutyl phenol of the probable formula:

ucn'omcmowmmQon is collected, I distilling above the latter tempera-'- ture and the major portion of it is obtained within the range of 170 C.-174 C. This fraction crystallizes within, the temperature range of 78 'C.-79 C. and may be further purified by crystallization from a petroleum solvent. The

, alkylated'phenol fraction weighs approximately made directly mm phenol by alkylating it with the required amount of trimethylethylene.

Example 3.The reaction of trimethylethylene with phenol at'50 C. whereby'material amounts oi.

ortho substitutedphenol resulted, was conducted as follows: 1740 grams of phenol were treated with 10 drops ofsulphuric acid and agitated at 50 C. under a reflux condenser. Trimethylethye lene vapor in the amount of 233 grams was then introduced into thereaction mass through an alundum distributor over a period 013 hours.

' A considerable amount of heat of reaction was 256 grams and represents a yield of 92.5% based upon the quantity of di-isobutylene employed.

that the loss of both phenol and di-isobutylene from resiniiflcationv or formation of other byproductsis practically negligible. If, in this reaction, isobutylene is slowlyintroduced into the generated and its was necessary occasionally to cool the reaction ilaskin order to maintain the temperature at the required value. In this example the agitation at this temperature was continued overnight (a periodof about 15 hours) and at the end of this period suillcient sodium carbonate'was added to neutralize the reaction product. The reaction mixture was then frac- "124 C.'-129- Cr This latter fraction was found phenol through a porous distributor tertiary 3o butylphenol is formed. If phenol is alkylated with di-isobutylene, or di-isobutyl phenol is heated with phenol at a fairly high temperature (e. g.

less) mono tertiary butylphenol results. By heating ortho tertiary butylphenol to the presence of atre e of a strongly acidic material, rearrangement to the para compound occurs.

butylphenol by subjecting approximately 350 grams of phenol to reactionwith 7'7 grams of diisobutylene in the presence of two or three crystals (approximately 0.2 gram) of iodine. The reaction is preferably conducted at a temperature of about 120 C. with agitation.

Example 2.A 306 gram portion of para tertiary amylphenol was treated with 6 drops of sulphuric acid and heated with agitation and under a reflux condenser to a temperature of 125 C.130 C. About 100 grams of gaseous trimethylethylene was then added over a period of five hours to the reaction mixture by bubbling it beneath the surface thereof through an alundum distributor (should the reaction slow down a few drops more of sulphuric acid is added). The reaction was then continued for approximately one hour longer, after which a little sodium carbonate was added to neutralize any acid present and the product was fractionally distilled under vacuum. Approximately 92 grams of para tertiary amylphenol, having a boiling point of 150 C.-165 C. at mm., were recovered. This was followed by an intermediate fraction amounting to approximately 17.5 grams having a boiling point of 165 C.-179 C. Di-amylphenol was obtained, boiling at 179 C.-185 C., in the amount of 258 grams. The residue after distillation amounted to '7 grams. The yield of di-amylphenol, based on the amylene used was approximately 77%. This yield can be increased to prac- I tically quantitative value by introducing the amylene at such rate that none of it escapes from temperatureof theorder oi. 140 C. or above in C. andcrystalli'zed at 885 C. The product'obj r h g It islikewise possible to obtain para di-isoto be completely soluble in dilute sodium hydrox ide and consisted essentially of ortho tertiary amylphenol. A fraction 0f"8-DProximate1y,14

grams, having a boilingrange of 129 (L-140 C., was then separated. Atthe latter temperature (140 C.) the product began to crystallize, indicating the presence of the para isomer. This iatter product was then collected as a 210 gram fraction boiling at a temperature of 144 Cr -146 tained by the present process, upon crystallization from petroleum ether, was found to'have a melting; pointof 93C. to 94 C. which agrees with the value given by the literature for para tertiary amylphenol.

The residue from the above fraction was transferred to a small flask and subjected to further distillation whereupon 63 gr. of liquid boiling at under otherwise identical conditions, the proportion of para isomers is slightly greater and the reaction vessel. lDi-amylphenol can also be a temperature of 167 C.-l68 C. under. 20 mm. pressure was obtained, and apparently comprised essentially diamylphenol. Accordingly, it appears that diamylphenol was formed at this temperature even in the presence of a large excess of phenol, but the proportions thereof, of course, can be further reduced by increasing the excess of phenol over the oleilne employed. The total yield of alkylated products is very nearly quantitative from the amylene used as well as the phenol. At the temperature of reaction employed, ortho and para tertiary amylphenol are obtained in about equal amounts. If the reaction is conducted at temperature of C.- C.

if the temperature is raised to near the boiling point of phenol (in the presence of an excess of the latter) the para tertiary amylphenol is formed almost exclusively.

The di-alkylated compounds (e. g. amylphenols) may be employed to alkylate further amounts of phenol and simultaneously they are partially de-alkylated to form mono-alkyl materials. The following example is illustrative of this process:

Example 4. Some diamyiphenol (051E111): CsH3OH 'was subjected to fractionation whereby a main fraction having a boiling point of accuser 159 C.-160 C. at 16 mm. absolute pressure was obtained. A 100 gram portion of this fraction was mixed with 547 grams of phenol and drops of sulphuric acid were added hereto. The mixture was then heated at a temperature of 170 C. overnight (about 15 hours)'and after the addition of enough sodium carbonate to neutralize the excess acid, it was subjected to fractionation. The para tertiary amylphenol was obtained as a 133 gram fraction, crystallizing at a temperature of 92 C. Substantially no residue remained after crystallization and this fact indicated that the diamylphenol was transformed substantially quantitatively into the mono tertiary amyl product. It is apparent irom-the discussions given above that the addition of the ortho isomeror of the ditertiary alkyl phenol to the main reaction will not increase or decrease the ratios of these components formed by the reaction since these are a function of the amount of phenol present and also the temperature conditions.

It will be apparent to those skilled in the art that the reaction is not limited to the use of the specific phenol disclosed in the above examples but that various substituted phenols having free ortho and or para positions which contain the essential nucleus of phenol, but in addition also contain various radicals and groups substituted for hydrogen in the benzene nucleus may be employed in any of the above examples. The following are typical of such phenols: hydroquinone, resorcinol, chlor-resorcinol, pyrocatechol, guaiacol, ortho or para chlorphenol, the cresols, naphthol, ortho or para phenylphenol, ortho or para benzylphenol, etc. These, of course, include the various isomers of these compounds which arepossible and known to the art. Likewise, substantially any of the ordinary tertiary olefine compounds may be reacted with any of the phenols herein listed. These include in addition to the ones given in the above examples: pinene, dimethylcyclohexene (derived from hydrogenated xylenols), as well as other tertiary Mixtures oi the various ingredients are also within the purview of the invention. For example, any two or more of the above phenols may be mixed together and then caused to react with any olefine or with mixtures thereof. Mm= tures of any of the tertiary olefines may also be reacted with any one of the phenols. Mixtures of olefines suitable for the reaction may well be obtained from the cracking of petroleum, a satisfactory mixture being obtained by treating the crude oleflnic product from the cracking operation with maleic anhydride to absorb dlolefines and then separating the desired product by fractionation or in other conventional manner.

The reactions described may be conducted in the presence of inert solvents or diluents including benzene. Where the reaction is conducted at relatively low temperatures, e. g., around 40 C. or below with phenols having high melting points, these solvents may be necessary in order to provide a homogeneous mixture. Similar results may be obtained by the addition of alkylated phenols (e. g., tertiary butylphenol) to the reaction mixture. These reduce the melting point and admit of operation at relatively low temperatures. Watenior example that occurring in most or wet phenol, may be present. Pressures above atmospheric may be used and are desirable where high temperatures are employed. Where high pressures and temperatures are employed in these reactions care must be observed to prevent the temperature from becoming so great as to cause charring of the ingredients.

In the examples given, sulphuric acid was indicated as constituting the catalyst. It is found to be-exceptionally efilcient for this purpose because it is highly active and is required in only minute traces. Also, the boiling point thereof 2574) and obtained by other methods.

is so high that it does not volatilize during the course of the reaction. It is likewise quite feasible to employ various derivatives of sulphuric acid in the same manner.- For example, alkyl sulphuric acid, sulphonic acids such as may be obtained by sulphonation of benzene, toluene. phenol, toluol, naphthol and the like may be employed.

It is even probable that at least at the higher temperatures of reaction, sulphuric acid reacts with the phenol or the olefine with which it contacts to form sulphonates or acid alkyl sulphates which then act as promoters of the reaction.

Sulphuric or sulphonic acid salts of weal: bases, a

such as urea or aniline are also applicable. Other strongly acid catalysts which may be used in mere traces are; phosphoric acid, phosphorous pentoxide, phosphorus trichloride, thionyl chloride, sulphur trioxide, hydrobromic acid, iodine and hydrochloric acid, and salts of easily bydrolyzable metals such as zinc chloride and aluminum chloride. Examples of the use of hydrogen chloride, hydrogen bromide, zinc chloride, aluminum chloride an small amounts of alkyl chloride are included in applicant's copending case Serial No. 727,881, filed May 28, 1934 (Examples 8 to 12) which application has issued as Patent No. 2,161,826.

Example 5. ,.-Seven hundred twenty-seven grams of dry br substantially dry phenol, such as is obtained by fractional distillation, are saturated at -85 C. with dry hydrogen chloride. For this purpose very little hydrogen chloride is necessary. Subsequently 100 grams of di-isobutylene, which may be obtained conveniently by condensing 2 mols of isobutylene and which may be represented structurally as follows:

depending upon the isomer form, are added while maintaining the previous temperature and agitated condition. From time to time a small amount of hydrogen chloride is introduced into the reaction mixture to assure saturation. After about 18 hours the product is fractionated. One hundred seventy grams of di-isobutyl phenol, boiling at approximately 157 C. at 18 mm., is obtained, practically no residue or by-products being formed. The product crystallizes at 82.5 C. which compares favorably with that recorded in the literature, 83 C. (J. A. C. S. 1933, page On crystallization from petroleum ether a product melting at 86 C. is obtained. The yield is equivalent to approximately 90% of theory based on the di-isobutylene and is practically quantitative based on the phenol consumed.

In lieu of di-lsobutylene one may employ homologues of di-isobutylene having tertiary olefinic linkage. Di-isobutylene is made by condensing two mols of isobutylene. Tri-isobutyi' ene, which may likewise be employed, is made by condensing three mols of isobutylene.

Example 6.Substitute a mol equivalent of triisobutylene for the di-isobutylene provided in Example and otherwise proceed as described in said Example 5.

Example 7.Substitute 88 grams of tetramethyl ethylene CH3 CH3 CH CH3 Cg: CH:

/CHC\ CH: CH:

alkyl halide. Thus, in lieu of gaseous hydrogen halide, one may add, either during the initial stages of the reaction or preferably progressively during the course of the reaction, a small amount of the tertiary alkyl chloride corresponding to the olefine and which may be obtained by reacting the olefine with concentrated hydrochloric acid as previously described in connection with Example 2 of the aforementioned application.-

Example 9.-One hundred sixty-five grams of resorcinol are dissolved in a sufiicient quantity of a mixture of ethyl and isopropyl ethers, the others being present in approximately equal parts by weight, to .form a true solution at about 70 The resulting solution is agitated at 70"-75 C. and treated with a mixture of 50 grams of diisobutylene and 5 grams of di-isobutyl chloride. The reaction is permitted to proceed for -14 hours, after which the reacted mixture is treated with suflicient water benzol to dissolve resorcinol and di-isobutyl resorcinol, respectively. aqueous resorcinol layer is drawn of! and the benzene layer is extracted three times with water to insure complete removal of the unreacted resorcinol. If desired, the resulting combined aqueous fractions may be extracted with benzol to removed any alkyl resorcinols which maybe contained therein. 78.5 grams of an oil boiling at 195-202 C. at 17 mm., which solidified upon cooling, is obtained. By crystallization one obtains a product which melts at 110C. This melting point, which is 8 higher than that reported in the literature, indicates that the product represented by the lower melting point was not very pure. The octyl resorcinol on chlorination has a very high phenol 'coeflicient, on Staphylococcus aureus. v

Examples 5, 6, '7, 8, and 9 are representative embodiments of my invention based on my discovery that olefines having. a tertiary olefinic linkage combine directly in good yields and without by-product formation to form the corresponding alkyl phenol.

My investigation has further disclosed that the di or poly iso-alkyl oleflnes such, for. example, as di-isobutylene or their hydrogen halide addition products, reactv at high temperatures with phenol to form, not the corresponding di or poly The alkyl phenol as might be expected, but the corresponding mono tertiary alkyl phenol such as tertiary butyl phenol.

Some of these di and poly iso-alkyl olefines 5 are obtained conveniently by condensing oleflnes, such as isobutylene, to form poly iso-alkyl 0lefines such as di-isobutylene, tri-isobutylene, etc. These materials and their corresponding alkyl halides react at elevated temperatures partly as the depolymerized alkyl halide which apparently combines with the phenol to form the corresponding alkyl phenol.

From the foregoing description it will be apparent that the quantity of carrier agent or catalyst required to effect the reaction of the unsaturated tertiary hydrocarbons with the phenols is so slight that the expense involved in the use thereof is negligible. Likewise, only a trace of alkali or sodium carbonate is required to effect neutralization thereof. Accordingly, the labor and loss attending washing of the product to remove the sodium salts is eliminated and distillation may be effected immediately after neutralization with sodium carbonate. The use of minute traces of sulphuric or sulphonic acids is further advantageous because little corrosion of the apparatus employed in conducting the reaction can occur. The formation of ethers and resins is also eliminated and exceptionally high yields of unusually pure product are thus obtained. Furthermore, by employing the principles of the invention it is possible to control the amounts of ortho or para alkylated products from it and similarly the yields of the dialkylated materials may be limited. The process is extremely simple in its nature and no complicated apparatus is required. For the above reasons it will be manifest that applicants process is highly convenient from a commercial standpoint.

In addition to uses as germicides, the reaction products are also susceptible of numerous other practical applications. For example, they may be condensed with aldehydes to form oil soluble artificial resins. They may also be sulfonated with concentrated sulfuric acid or oleum and then neutralized with an alkali or alkali earth metal to form wetting agents of exceptional merit. For this purpose the di-alkyl phenols such as di-amyl phenol are of particular value.

.The method of forming the sulphuric acid derivatives, such as the sulphonate, of the herein described compounds is well understood. Likewise, the formation of the alkali or alkaline earth metal salts of these compounds is well understood. For example, to about 25 parts of the I alkylated phenol which has been chilled to approximately 510 C. are added 5 parts of 95% sulphuric acid over a period of approximately 10 minutes. Then 30 parts of oleum (10-20%) are added over a period of 1 to 2 hours while main- 4 taining the reaction mass at reaction temperature which will usually range from -70 C. or higher. phuric acid is desirable and the yields are sometimes improved ,by stirring for approximately 1 hour after the sulphuric acid has been added. The reaction mixture is then diluted with an equal volume of water and neutralized with so- 1 carbonate and evaporated to dryness. If desir d, this neutralized aqueous solution may be evapo ated by spray-drying. In either of the ,dryin steps, the resultant product is the sodium phenol; Another way to separate the alkali metal Stirring during the addition of the sulof sulphuric acid derivative of the alkyl salts of these sulphuric acid derivatives is to dilute the reaction mass with about an equal volume of water, salt out the reaction product by adding sodium chloride, and then filtering off the alkali metal salt of the sulphuric acid derivative of the alkyl phenol.

Although only certain preferred embodiments of the invention have been described it is to be understood that these are merely illustrative and that numerous modifications may be made therein without departure from the spirit of the invention or the scope of the appended claims;

This application is a continuation-in-part of my copending application, Serial No. 778, filed January 7, 1935, which is now U. S. Patent 2,189,805, February 13, 1940.

What I claim is:

1. A detergent aid particularly useful as a wetting agent comprising essentially an alkali metal salt of the sulphuric acid derivative of a reaction product of acyclic hydrocarbon polymers having a molecular weight between about 100 and about 224 and a phenol.

2. Alkali metal salt of sulphuric acid derivative of an alkyl phenol, said alkyl group correting agent comprising essentially sulphuric acid derivative of a reaction product of acyclic hydrocarbon polymers. having a molecular weight between about 100 and about 224 and a phenol.

5. A detergent and wetting agent comprising essentially an alkali metal salt of the sulphuric acid derivative of a reaction product of di-isobutylene and phenol.

6. Alkali-metal salt of sulphuric acid derivative of an alkyl phenol, having pronounced wetting and detergent properties, the said alkyl group corresponding to an acyclic hydrocarbon polymer, having a molecular weight not higher than about 224, ofisobutylene.

'7. Alkali metal salt of sulphuric acid tive 01' an alkyl phenol, having pronounced wetting and detergent properties, the said alkyl group corresponding to an acyclic hydrocarbon polymer,v having a molecular weight between about 100 and 224, produced from an olefin-containing fraction of cracked petroleum gases containing a maior proportion of hydrocarbons of four carbon atoms per molecule.'

8. A detergent aid particularly useful as a wetting agent comprising, essentially an alkali metal salt of the sulphuric acid derivative of a reaction product of acyclic hydrocarbon polymers having a molecular weight between about 100 and about 224 and phenol.

9. A detergent and wetting agent comprising essentially an alkali metal salt of the sulphuric acid derivative of a reaction product of tri-isobutylene and phenol.

LUCAS P. KYRIDES.

deriva- 

